# US 11,111,325 B2 · Polymerization processes

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- Number: US 11,111,325 B2
- Document ID: US11111325B2
- Status: Granted
- Kind: B2
- Application number: 16/191,385
- Filed: 2018-11-14
- Published: 2019-05-16
- Granted: 2021-09-07
- Earliest claimed: 2017-11-15
- Assignees: ExxonMobil Chemical Patents Inc.
- Applicants: ExxonMobil Chemical Patents Inc.
- Inventors: Donna J. Crowther; Timothy M. Boller; Richard B. Pannell; Jeanette M. Diop; Wen Li
- Web page: https://patentgrep.com/patent/US11111325B2

## CPC

- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F 4/65904: {in combination with another component of C08F4/64}
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F 4/65916: {supported on a carrier, e.g. silica, MgCl2, polymer}
- C08F 4/6592: containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F 4/65927: {two cyclopentadienyl rings being mutually bridged}
- C08F 2420/02: Cp or analog bridged to a non-Cp X anionic donor
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

Polymerization processes to produce polyolefin polymers, for example, polyethylene polymers, from catalyst systems comprising one or more olefin polymerization catalysts and at least one activator are provided. The polyolefin polymers may have a Broad Orthogonal Composition Distribution (BOCD).

## Claims

### Claim 1

A polymerization process to produce a polyethylene polymer, the process comprising contacting a catalyst system comprising a product of a combination of one or more metallocene catalysts, at least one activator, and at least one support, with ethylene and one or more C3-C10 alpha-olefin comonomers under polymerizable conditions including a temperature range of from 10° C. to 75° C., to produce the polyethylene polymer;
wherein the polyethylene polymer has a broad orthogonal composition distribution (BOCD) and furthermore has a density of from 0.890 g/cm3 to 0.950 g/cm3, and
further wherein the one or more metallocene catalysts comprises:
(A) a compound represented by Formula (I):
TyCpmM6GnX5q (I),
wherein each Cp is, independently, a cyclopentadienyl group which may be substituted or unsubstituted, M6 is a Group 4 transition metal, G is a heteroatom group represented by the Formula JR*z where J is N, and R* is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, cyclooctyl, cyclododecyl, decyl, undecyl, dodecyl, adamantyl or an isomer thereof and z is 1 or 2, T is a bridging group, and y is 1, X5 is a leaving group, and m=1, n=1, q=0, 1, 2 or 3, and the sum of m+n+q is equal to the oxidation state of the transition metal; and/or
(B) one or more of the following compounds:
dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)titanium dimethyl;
dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)titanium dichloride;
dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)titanium dimethyl; dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)titanium dichloride; μ-(CH3)2Si(cyclopentadienyl)(1-adamantylamido)M7(R15)2; μ-(CH3)2Si(3-tertbutylcyclopentadienyl)(1-adamantylamido)M7(R15)2; μ-(CH3)2C(tetramethylcyclopentadienyl)(1-adamantylamido)M7(R15)2; μ-(CH3)2Si(tetramethylcyclopentadienyl)(1-adamantylamido)M7(R15)2; μ-(CH3)2C(tetramethylcyclopentadienyl)(1-tertbutylamido)M7(R15)2; μ-(CH3)2Si(tetramethylcyclopentadienyl)(1-tertbutylamido)M7(R15)2; μ-(CH3)2Si(fluorenyl)(1-tertbutylamido)M7(R15)2; μ-(CH3)2Si(tetramethylcyclopentadienyl)(1-cyclododecylamido)M7(R15)2; or
μ-(C6H5)2C(tetramethylcyclopentadienyl)(1-cyclododecylamido)M7(R15)2,
where M7 is selected from a group consisting of Ti, Zr, and Hf and R15 is selected from halogen or C1-C5 alkyl.

### Claim 2 (depends on 1)

The process of claim 1, wherein the temperature range is from 10° C. to 70° C.

### Claim 3 (depends on 1)

The process of claim 1, wherein the temperature range is from 10° C. to 65° C.

### Claim 4 (depends on 1)

The process of claim 1, wherein the temperature range is from 20° C. to 60° C.

### Claim 5 (depends on 1)

The process of claim 1, wherein the at least one activator comprises an alumoxane, an aluminum alkyl, an ionizing activator, or mixtures thereof.

### Claim 6 (depends on 1)

The process of claim 1, wherein the at least one activator comprises methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane, isobutylalumoxane, alkylalumoxane, modified alkylalumoxane, or mixtures thereof.

### Claim 7 (depends on 1)

The process of claim 1, wherein the at least one support comprises talc, clay, silica, alumina, silica-alumina, magnesia, zirconia, iron oxides, boria, calcium oxide, zinc oxide, barium oxide, thoria, aluminum phosphate gel, polyvinylchloride, substituted polystyrene, functionalized or crosslinked organic supports, polystyrene divinyl benzene, graphite, or mixtures thereof.

### Claim 8 (depends on 1)

The process of claim 1, wherein the one or more metallocene catalysts comprises hafnium.

### Claim 9 (depends on 8)

The process of claim 8, wherein the at least one activator comprises aluminum and an aluminum to hafnium ratio is at least 150 to 1.

### Claim 10 (depends on 8)

The process of claim 8, wherein the at least one activator comprises aluminum and an aluminum to hafnium ratio is at least 250 to 1.

### Claim 11 (depends on 8)

The process of claim 8, wherein the at least one activator comprises aluminum and an aluminum to hafnium ratio is at least 1,000 to 1.

### Claim 12 (depends on 1)

The process of claim 1, wherein the catalyst system comprises two or more different metallocene catalysts.

### Claim 13 (depends on 1)

The process of claim 1, wherein the polymerization process is a gas phase fluidized bed, solution phase, and/or a slurry phase polymerization process.

### Claim 14 (depends on 1)

The process of claim 1, wherein the polymerization process is a gas phase fluidized bed polymerization process and further comprises an inert condensing agent comprising n-butane, isobutane, n-pentane, neopentane, isopentane, n-hexane, isohexane, n-heptane, n-octane, or mixtures of thereof.

### Claim 15 (depends on 1)

The process of claim 1, wherein the polyethylene polymer has a density of from 0.910 g/cm3 to 0.940 g/cm3.

### Claim 16 (depends on 1)

The process of claim 1, wherein the polyethylene polymer has a melt index (I2) of from 0.10 g/10 min to 10 g/10 min.

### Claim 17 (depends on 1)

The process of claim 1, wherein the polyethylene polymer has a melt index (I2) of from 0.50 g/10 min to 7 g/10 min.

### Claim 18 (depends on 1)

The process of claim 1, wherein the one or more metallocene catalysts comprises a compound represented by Formula (I).

### Claim 19 (depends on 18)

The process of claim 18, wherein each Cp is a cyclopentadienyl, indenyl, or fluorenyl, which may be substituted or unsubstituted, each M6 is titanium, zirconium, or hafnium, and each X5 is, independently, a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group.

### Claim 20 (depends on 1)

The process of claim 1, wherein the catalyst system comprises a product of a combination of a single metallocene catalyst, at least one activator, and at least one support, and furthermore wherein the metallocene catalyst is not bis(n-propyl cyclopentadienyl) hafnium dichloride.

### Claim 21 (depends on 20)

The process of claim 20, wherein the metallocene catalyst is furthermore not bis(n-propyl cyclopentadienyl) zirconium dichloride.

### Claim 22 (depends on 1)

The process of claim 1, wherein the metallocene catalyst is not bis(n-propyl cyclopentadienyl) hafnium Xn, wherein Xn is selected from the group consisting of halogen ions, hydrides, C1-12 alkyls, C2-12 alkenyls, C6-12 aryls, C7-20 alkylaryls, C1-12 alkoxys, C6-16 aryloxys, C7-18 alkylaryloxys, C1-12 fluoroalkyls, C6-12 fluoroaryls, and C1-12 heteroatom-containing hydrocarbons.